JPH02188494A - Production of thin film of diamond or the like and device therefor - Google Patents
Production of thin film of diamond or the like and device thereforInfo
- Publication number
- JPH02188494A JPH02188494A JP1006292A JP629289A JPH02188494A JP H02188494 A JPH02188494 A JP H02188494A JP 1006292 A JP1006292 A JP 1006292A JP 629289 A JP629289 A JP 629289A JP H02188494 A JPH02188494 A JP H02188494A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- diamond
- gas
- film forming
- opening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 109
- 239000010432 diamond Substances 0.000 title claims abstract description 48
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 239000010408 film Substances 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 47
- 238000005520 cutting process Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- -1 hydrogen compound Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PDKAXHLOFWCWIH-UHFFFAOYSA-N 1,1-dichlorobuta-1,3-diene Chemical compound ClC(Cl)=CC=C PDKAXHLOFWCWIH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 239000010727 cylinder oil Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000010649 ginger oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はダイヤモンド類薄膜の製造方法および製造装置
に関し、さらに詳しく言うと、膜厚の均一性に優れると
共にｉｌｍを生しにくくて、たとえば耐久性に優れたダ
イヤモンド類薄膜付き切削工具類に好適に利用すること
のできるダイヤモンド類ｄｔｊＷ２を気相法により容易
に形成することのできるダイヤモンド類薄膜の製造方法
と、この製造方法において好適に使用することのてきる
ダイヤモンド類薄膜の製造袋δとに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method and apparatus for producing a diamond-based thin film, and more specifically, the present invention relates to a method and apparatus for producing a diamond-based thin film, and more specifically, it has excellent film thickness uniformity, is difficult to produce ilm, and has excellent durability, for example. A method for producing a diamond-like thin film that can be easily formed by a vapor phase method, and a method for producing a diamond-like thin film, which can be suitably used for cutting tools with a diamond-like thin film having excellent properties, and a diamond-like thin film suitable for use in this production method. The present invention relates to a manufacturing bag δ for a diamond thin film.
［従来技術および発明か解決しようとする課題］ダイヤ
モンド膜またはダイヤモンド状炭素膜は硬度、耐摩耗性
、電気絶縁性、熱伝導性および固体潤滑性などに優れて
いることから、たとえば切削工具類、耐摩耗性機械部品
等の各種部材のハードコート材や電子材料などに利用さ
れつつある。[Prior Art and Problems to be Solved by the Invention] Diamond films or diamond-like carbon films have excellent hardness, wear resistance, electrical insulation, thermal conductivity, solid lubricity, etc. It is being used as a hard coat material for various parts such as wear-resistant mechanical parts, and as electronic materials.
そして、このダイヤモンド類薄膜の製造方法に乞いては
一般に気相法か採用されている。A vapor phase method is generally adopted as a manufacturing method for this diamond thin film.
たとえば、特開昭６３−１６６７：ｌ：１号公報におい
ては１反応槽内に金属もしくはその金属化合物を均一に
点在した基板を配置して該基板を５００乃至１３００℃
に加熱した後、該反応槽内に少なくとも水素原子、炭素
原子、酸素原子を含むダイヤモンド生成用ガスを導入す
るとともに該ガスを活性化させて該基板表面にダイヤモ
ンドを析出させるダイヤモンド膜の製造方法が開示され
ている。For example, in Japanese Patent Application Laid-Open No. 63-1667:l:1, a substrate on which metals or metal compounds thereof are uniformly dotted is placed in one reaction tank, and the substrate is heated at 500 to 1300°C.
A method for producing a diamond film includes introducing a diamond-forming gas containing at least hydrogen atoms, carbon atoms, and oxygen atoms into the reaction tank and activating the gas to deposit diamond on the surface of the substrate. Disclosed.
しかしながら、この方法においては、平板状の支持台上
にダイヤモンド膜を形成すべき基板を載置するので、ダ
イヤモンド生成用ガスを、たとえばマイクロ波や高周波
により活性化すると、前記支持台上に突出した基板のエ
ツジ部にプラズマが局所的に集中してしまうという問題
がある。However, in this method, the substrate on which the diamond film is to be formed is placed on a flat support, so when the diamond-forming gas is activated, for example, by microwaves or high frequency, the diamond film protruding onto the support is activated. There is a problem in that plasma is locally concentrated at the edge of the substrate.
そして、たとえばこの方法を採用してダイヤモンド類薄
膜付き切削工具を製造すると、切削工具のエツジ部に局
所的にプラズマが集中し、この部分において膜厚が特に
厚くなり、膜厚が不均一となって熱応力や内部応力に急
激な変化を生ずるのて、切削工具において最も重要なエ
ツジ部においてダイヤモンド類薄膜が剥離し易いという
耐久性の乏しいダイヤモンド類薄膜付き切削工具しか得
られない。For example, if this method is used to manufacture a cutting tool with a diamond-like thin film, plasma will be locally concentrated at the edge of the cutting tool, and the film will be particularly thick in this area, resulting in uneven film thickness. As a result, a cutting tool with a diamond-like thin film having poor durability can be obtained, in which the diamond-like thin film easily peels off at the most important edge portion of the cutting tool.
また、特開昭６３−２８５１９２号公報においては、炭
素源の化合物及び水素類の化合物を用いて気相法により
ダイヤモンドを合成する方法において、前記炭素源の化
合物及び水素源の化合物のうち一部乃至全部を励起する
前に予め加熱するダイヤモンド合成法が開示されている
。Furthermore, in JP-A No. 63-285192, in a method for synthesizing diamond by a gas phase method using a carbon source compound and a hydrogen compound, some of the carbon source compound and hydrogen source compound are A diamond synthesis method is disclosed in which the diamond is preheated before being fully excited.
しかしながら、この方法においても、平板状の支持台上
にダイヤモンド膜を形成すべき基板を載置することに変
わりはないので、炭素源の化合物及び水素源の化合物を
、たとえばマイクロ波や高周波により励起すると、プラ
ズマが局所的に集中するという前述の問題かある。However, even in this method, the substrate on which the diamond film is to be formed is placed on a flat support, so the carbon source compound and the hydrogen source compound are excited by microwaves or high frequencies. Then, there is the problem mentioned above that the plasma is locally concentrated.
すなわち、気相法を採用する従来のダイヤモンド膜の製
造方法、特にプラズマ法による製造方法においては、プ
ラズマがエツジ部に局所的に集中するという問題があり
、中でも、プラズマによって基板の発熱を招くマイクロ
波プラズマ法、高周波プラズマ法によっては膜厚の均一
性に優れて剥離の生しにくいダイヤモンド膜を製造する
ことは困難である。In other words, in conventional diamond film manufacturing methods that employ the vapor phase method, especially in the plasma method, there is a problem in that plasma is locally concentrated at the edges. It is difficult to produce a diamond film with excellent uniformity in film thickness and resistant to peeling by the wave plasma method or high frequency plasma method.
本発明は、前記の事情に基いてなされたものである。The present invention has been made based on the above circumstances.
本発明の目的は、膜厚の均一性に優れると共に′Ａ離が
少なくて、たとえば耐久性に優れたダイヤモンド類薄膜
付き切削工具類に好適に利用することのできるダイヤモ
ンド類薄膜を気相法により容易に形成することのできる
ダイヤモンド類薄膜の製造方法と、この方法において好
適に使用することのできるダイヤモンド類薄膜の製造装
置とを提供することにある。An object of the present invention is to produce a diamond-like thin film by a vapor phase method, which has excellent film thickness uniformity and low A separation, and can be suitably used, for example, in cutting tools with a diamond-like thin film coated with excellent durability. It is an object of the present invention to provide a method for manufacturing a diamond-based thin film that can be easily formed, and an apparatus for manufacturing a diamond-based thin film that can be suitably used in this method.
［課題を解決するための手段］
前記課題を解決するために本発明者らが鋭意検討を重ね
た結果、気相法を採用するダイヤモンド類薄膜の製造方
法においては、特定の状態に保持した薄膜被形成部材の
薄膜被形成面に、炭素源ガスを含有する原料ガスを励起
させて得られるガスを接触させると、プラズマの局所的
な集中を有効に防止することが可億であり、膜厚均一性
に優れ、！ｊｑｆａを生じにくく、たとえば耐久性に優
れた高性能のダイヤモンド類ｆ＝ＨＩＱ付き切削工具類
に好適に利用することのできるダイヤモンド類薄膜を容
易に効率良く形成することかてきること、およびこの特
定の製造方法においては特定の保持部材を備える特定の
製造装置を好適に使用することかできることを見い出し
て、本発明に到達した。[Means for Solving the Problems] As a result of intensive studies by the present inventors to solve the above-mentioned problems, it has been found that in a method for manufacturing a diamond thin film that employs a vapor phase method, a thin film that is maintained in a specific state is When a gas obtained by exciting a raw material gas containing a carbon source gas is brought into contact with the surface on which a thin film is to be formed of a member to be formed, local concentration of plasma can be effectively prevented, and the film thickness can be reduced. Excellent uniformity! It is possible to easily and efficiently form a diamond-based thin film that does not easily cause jqfa and can be suitably used, for example, in durable, high-performance diamond-based cutting tools with f = HIQ, and this specification The present invention was achieved by discovering that a specific manufacturing device equipped with a specific holding member can be suitably used in the manufacturing method.
請求項１の発明の構成は、炭素源ガスを含有するａ料ガ
スを励起して得られるガスを、薄膜被形成部材の薄膜被
形成面と保持部材の表面とが同−而を形成するべく前記
保持部材の開口部内に保持された前記薄膜被形成部材の
前記薄膜被形成面に接触させて、前記−！脱核形成面上
にダイヤモンド膜および／またはダイヤモンド状炭素膜
を形成することを特徴とするダイヤモンド類薄膜の製造
方法であり、
請求項２の発明の構成は、薄膜被形成部材を保持する開
口部を有すると共に、前記Ｑ脱核形成部材の薄膜被形成
面と同一面を形成する開口部開設面を有する保持部材と
、放電装置とを備えることを特徴とするダイヤモンド類
薄膜の製造装置であり、
請求項３の発明の構成は、前記開口部が貫通孔である請
求項２に記載のダイヤモンド類８膜の製造装置である。The structure of the invention of claim 1 is such that the gas obtained by exciting the a-material gas containing the carbon source gas is formed on the thin film forming surface of the thin film forming member and the surface of the holding member. The -! by bringing the -! A method for manufacturing a diamond-like thin film, characterized in that a diamond film and/or a diamond-like carbon film is formed on a denucleation surface, and the invention according to claim 2 has an opening for holding a member on which a thin film is formed. and a holding member having an opening surface forming the same surface as the thin film forming surface of the Q denucleation forming member, and a discharge device, A third aspect of the present invention provides the apparatus for producing a diamond-type 8 film according to the second aspect, wherein the opening is a through hole.
請求項１の発明の方法においては、炭素源ガスを含有す
る原料ガスを反応室内に導入する。In the method according to the first aspect of the invention, a raw material gas containing a carbon source gas is introduced into a reaction chamber.
使用に供される前記原料ガスは、少なくとも炭素源ガス
を含有するものてあればよいが、少なくとも炭素原子と
水素原子とを含むガスが好ましくく、炭素原子と水素原
子と酸素原子とを含むガスは特に好ましい。The raw material gas to be used may contain at least a carbon source gas, but preferably a gas containing at least a carbon atom and a hydrogen atom, and a gas containing a carbon atom, a hydrogen atom, and an oxygen atom. is particularly preferred.
具体的には、前記３１４ガスとして、たとえば炭素源ガ
スと水素ガスとの混合ガスを挙げることかできる。Specifically, the 314 gas may be, for example, a mixed gas of carbon source gas and hydrogen gas.
また、所望により、前記原料ガスとともに、不活性ガス
等のキャリヤーガスを用いることもできる。Further, if desired, a carrier gas such as an inert gas may be used together with the raw material gas.
前記炭素源ガスとしては、各種炭化水素、含酸素化合物
、含窒素化合物等のガスを使用することができる。As the carbon source gas, gases such as various hydrocarbons, oxygen-containing compounds, nitrogen-containing compounds, etc. can be used.
炭化水素化合物としては１例えばメタン、エタン、プロ
パン、ブタン等のパラフィン系炭化水素：エチレン、プ
ロピレン、ブチレン等のオレフィン系炭化水素：アセチ
レン、アリレン等のアセチレン系炭化水素：ブタジェン
等のジオレフィン系炭化水素；シクロプロパン、シクロ
ブタン、シクロペンタン、シクロヘキサン等の脂垣式炭
化水素二ジクロブタジェン、ベンゼン、トルエン、キシ
レン、ナフタレン等の芳香族炭化水素二塩化メチル、臭
化メチル、塩化メチレン、四塩化炭素等のハロゲン化炭
化水素などを挙げることかできる。Examples of hydrocarbon compounds include: Paraffinic hydrocarbons such as methane, ethane, propane, and butane; Olefinic hydrocarbons such as ethylene, propylene, and butylene; Acetylenic hydrocarbons such as acetylene and arylene; Diolefinic hydrocarbons such as butadiene; Hydrogen: Aromatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane Aromatic hydrocarbons such as dichlorobutadiene, benzene, toluene, xylene, and naphthalene Methyl dichloride, methyl bromide, methylene chloride, carbon tetrachloride Examples include halogenated hydrocarbons such as.
含酸素化合物としては、例えばアセトン、ジエチルケト
ン、ベンゾフェノン等のケトン類：メタノール、エタノ
ール、プロパツール、ブタノール等のアルコール類：メ
チルエーテル、エチルエーテル、エチルメチルエーテル
、メチルプロピルエーテル、エチルプロピルエーテル、
フェノールエーテル、アセタール、環式エーテル（ジオ
キサン、エチレンオキシド等）のエーテル類：アセトン
、ビナコリン、メチルオキシド、芳香族ケトン（アセト
フェノン、ベンゾフェノン等）、ジケトン、環式ケトン
等のケトン類：ホルムアルデヒド、アセトアルデヒド、
ブチルアルデヒド、ベンズアルデヒド等のアルデヒド類
：ギ酸、酢酸、プロピオン酸、コハク酸、ｍ酸、シュウ
酸、酒石酸、ステアリン酸専の有機酸類；酢酸メチル、
酢酸エチル等の酸エステル類；エチレングリコール、ジ
エチレングリコール等の二価アルコール類、−酸化炭素
、二酸化炭素等を挙げることができる。Examples of oxygen-containing compounds include ketones such as acetone, diethyl ketone and benzophenone; alcohols such as methanol, ethanol, propatool and butanol; methyl ether, ethyl ether, ethyl methyl ether, methyl propyl ether, ethyl propyl ether;
Ethers such as phenol ethers, acetals, and cyclic ethers (dioxane, ethylene oxide, etc.): Ketones such as acetone, vinacolin, methyl oxide, aromatic ketones (acetophenone, benzophenone, etc.), diketones, and cyclic ketones: formaldehyde, acetaldehyde,
Aldehydes such as butyraldehyde and benzaldehyde: formic acid, acetic acid, propionic acid, succinic acid, m-acid, oxalic acid, tartaric acid, stearic acid; organic acids such as methyl acetate,
Examples include acid esters such as ethyl acetate; dihydric alcohols such as ethylene glycol and diethylene glycol; -carbon oxide and carbon dioxide.
含窒素化合物としては、例えばトリメチルアミン、トリ
エチルアミンなどのアミン類等を挙げることができる。Examples of the nitrogen-containing compound include amines such as trimethylamine and triethylamine.
また、前記炭素源ガスとして、単体ではないが、消防法
に規定される第４類危険物；ガソリンなどの第１石油類
、ケロシン、テレピン油、しょう脳油、松根油などの第
２石油類、重油などの第３石油類、ギヤー油、シリンダ
ー油などのｔ５４石油類などのガスをも使用することか
てきる。また前記各種の炭素化合物を混合して使用する
こともできる。In addition, as the carbon source gas, although not a single substance, class 4 dangerous substances specified in the Fire Service Act; class 1 petroleum such as gasoline, class 2 petroleum such as kerosene, turpentine, ginger oil, and pine oil; It is also possible to use gases such as tertiary petroleum such as heavy oil, T54 petroleum such as gear oil and cylinder oil. It is also possible to use a mixture of the various carbon compounds mentioned above.
これらの炭素源ガスの中でも、常温で気体または蒸気圧
の高いメタン、エタン、プロパン等のパラフィン系炭化
水素；あるいはアセトン、ベンゾフェノン等のケトン類
、メタノール、エタノール等のアルコール類、−酸化炭
素、二酸化炭素ガス等の含酸素化合物か好ましい。Among these carbon source gases, paraffin hydrocarbons such as methane, ethane, and propane, which are gases or have high vapor pressure at room temperature; or ketones such as acetone and benzophenone, alcohols such as methanol and ethanol, carbon oxide, and carbon dioxide. Oxygen-containing compounds such as carbon gas are preferred.
前記水素ガスには、特に制限かなく、たとえば石油類の
ガス化、天然ガス、水性ガスなどの変成、水の電解、鉄
と水蒸気との反応、石炭の完全ガス化などにより得られ
るものを充分に精製したものを用いることができる。There are no particular restrictions on the hydrogen gas, and hydrogen gas obtained by, for example, gasification of petroleum, metamorphosis of natural gas, water gas, etc., electrolysis of water, reaction between iron and steam, complete gasification of coal, etc. is sufficient. It can be used after being purified.
前記水素ガスを構成する水素は励起されることにより原
子状水素を形成する。Hydrogen constituting the hydrogen gas is excited to form atomic hydrogen.
この原子状水素は、硬質炭素の析出と同時に析出する黒
鉛構造の炭素等の非硬質炭素を除去する作用を有する。This atomic hydrogen has the effect of removing non-hard carbon, such as graphite-structured carbon, which is precipitated at the same time as hard carbon is precipitated.
前記原料ガスの合計ＩＩ！、量は、通常、１〜１．００
０ＳＣＣＭ、好ましくはｌＯ〜２００ ＳＣＣＭである
。Total of the raw material gas II! , the amount is usually 1 to 1.00
0 SCCM, preferably 10 to 200 SCCM.
また、前記原料ガスに炭素源ガスと水素ガスとの混合ガ
スを使用する場合の炭素源ガスと水素ガスとの混合比は
、通常、前記炭素源ガスと前記水素ガスとの合計流量に
対して前記炭素源ガスの流量が０．１〜９０％、好まし
くは０．２〜８０％、さらに好ましくは０．２〜６０％
である。なお、この混合比は炭素源ガスの種類によって
も異なるので、最適な組合せを適宜に決定すればよい。Furthermore, when a mixed gas of a carbon source gas and hydrogen gas is used as the raw material gas, the mixing ratio of the carbon source gas and hydrogen gas is usually determined relative to the total flow rate of the carbon source gas and the hydrogen gas. The flow rate of the carbon source gas is 0.1 to 90%, preferably 0.2 to 80%, more preferably 0.2 to 60%.
It is. Note that this mixing ratio varies depending on the type of carbon source gas, so the optimum combination may be determined as appropriate.
混合ガス中の炭素源ガスの流量が０．１％よりも少ない
と、ダイヤモンド類薄膜が成膜されなかったり、ダイヤ
モンド類ｊ膜がたとえ成膜されてもその成膜速度が著し
く小さくなったりする。If the flow rate of the carbon source gas in the mixed gas is less than 0.1%, a diamond-like thin film may not be formed, or even if a diamond-like film is formed, the deposition rate will be significantly slow. .
本発明の方法において使用に供される前記薄膜被形成部
材の材質には特に制限がなく、たとえばシリコン、アル
ミニウム、チタン、タングステン、モリブデン、コバル
ト、クロムなどの金属、これらの酸化物、窒化物および
炭化物、これらの合金、ＷＣ−Ｃｏ系、ｗＣ−ＴｉＣ−
Ｃｏ系、ＷＣ−ＴｉＣ−ＴａＣ−Ｃｏ系などの超硬合金
、＾ｌＪｉ −Ｆｅ系、ＴｉＣ−Ｎｉ 系、Ｔ １ｃ−
Ｃｏ系、ＴｉＣ−ＴｉＮ系、８４Ｃ−Ｆｅ系等のサーメ
ット、さらには各種ガラス、セラミックスや樹脂などの
中から選ばれた任意のものを用いることができる。There is no particular restriction on the material of the thin film forming member used in the method of the present invention, and examples thereof include metals such as silicon, aluminum, titanium, tungsten, molybdenum, cobalt, and chromium, their oxides, nitrides, and Carbide, alloy of these, WC-Co system, wC-TiC-
Cemented carbide such as Co type, WC-TiC-TaC-Co type, ^lJi -Fe type, TiC-Ni type, T1c-
Any cermet selected from Co-based, TiC-TiN-based, 84C-Fe-based cermets, various glasses, ceramics, resins, etc. can be used.
また、前記ＩＩＩ膜被膜成形成部材状についても特に制
限はなく、たとえば板状、チップ状（三角、四角）、ド
リル等の特殊形状などの任意の形状のものを用いること
ができる。Further, the shape of the member for forming the III film is not particularly limited, and any shape may be used, such as a plate, a chip (triangular or square), or a special shape such as a drill.
特に、前記薄膜被形成部材が超硬合金、サーメットなど
からなる工具類であると１本発明の方法により得られる
ダイヤモンド膜および／またはダイヤモンド状炭素膜を
形成してなる基材を、そのまま工具類として用いること
が回旋である。そのような工具類としては、たとえばソ
リッドトリル等の穴あけ工具ニ一般旋削用、カッター用
等のチップ：エンドミル；バイトなどの各種切削工具を
好適例として挙げることがてきる。In particular, when the member on which the thin film is formed is a tool made of cemented carbide, cermet, etc., the base material formed with the diamond film and/or diamond-like carbon film formed by the method of the present invention can be directly used as a tool or the like. Rotation is used as a rotation. Suitable examples of such tools include various cutting tools such as drilling tools such as solid trills, tips for general turning and cutters, end mills, and bits.
本発明の方法においては、前記ＦＪ膜膜形形成部材薄膜
被形成面と保持部材の表面とが同一面を形成するべく前
記保持部材の開口部内に保持された前記＠脱液形成部材
の前記薄膜被形成面に、前記原料ガスを励起して得られ
るガスを接触させて。In the method of the present invention, the thin film of the @ deliquification forming member is held within the opening of the holding member so that the thin film forming surface of the FJ film membrane forming member and the surface of the holding member form the same surface. A gas obtained by exciting the source gas is brought into contact with the surface to be formed.
前記薄膜被形成部材の前記薄膜被形成面上にダイヤモン
ド薄膜および／またはダイヤモンド状炭素薄膜を形成す
る。A diamond thin film and/or a diamond-like carbon thin film is formed on the thin film forming surface of the thin film forming member.
すなわち１本発明の方法においては、たとえば第１図に
示すように、１３膜被形成部材１を、保持部材２の開口
部内３て、薄膜被形成部材ｌの薄膜被形成面ｌＯと、保
持部材２の表面２０とが同一面を形成するように保持す
ることが重要てあり、保持部材２の開口部３内で露出し
た薄膜被形成面ｌＯ上にダイヤモンド薄膜および／また
はダイヤモンド状炭素薄膜が形成される。That is, in the method of the present invention, for example, as shown in FIG. It is important that the diamond thin film and/or the diamond-like carbon thin film be formed on the thin film formation surface lO exposed within the opening 3 of the holding member 2. be done.
ここで、「同一面」とは実質的にＢ膜板形成部材ｌの薄
膜被形成面１０と保持部材２の開口部３以外の表面２０
とに段差を生じないことを言う、ただし、本発明の目的
を阻害しない範囲で前記の段差が生じていてもよい、そ
のような段差は、薄膜被形成部材の大きさ、材質等にも
よるが、通常、ｌ」−以内である。また、保持部材と薄
膜被形成部材のエツジ部との隙間は、通常、ｌｌ１１以
内てあり、エツジ部の側面まて薄Ｉ′ｔ！２を形成でき
ることか必要である。いずれにしても、本発明の方法は
、保持部材を特定形状にすることにより、薄膜被形成部
材にみかけのエツジ部を形成しないことに特長を有する
。したかって、前記の段差および前記の隙間が、前記の
範囲を超えると、前記原料ガスを励起して生じるプラズ
マかエツジ部に局所的に集中して、膜厚の均一性に優れ
ると共に剥離の少ないダイヤモンド薄膜および／または
ダイヤモンド状炭素薄膜を製造することかできない。Here, "the same surface" is substantially the thin film forming surface 10 of the B membrane plate forming member l and the surface 20 of the holding member 2 other than the opening 3.
However, the above-mentioned step may occur within the range that does not impede the purpose of the present invention. Such a step depends on the size, material, etc. of the member on which the thin film is formed. is usually within l''. Further, the gap between the holding member and the edge portion of the thin film forming member is usually within 111, and the side surface of the edge portion is thin I't! It is necessary to be able to form 2. In any case, the method of the present invention is characterized in that, by forming the holding member into a specific shape, no apparent edge portion is formed on the member on which the thin film is to be formed. Therefore, if the step and the gap exceed the above range, the plasma generated by exciting the raw material gas will be locally concentrated at the edge, resulting in excellent film thickness uniformity and less peeling. It is not possible to produce diamond thin films and/or diamond-like carbon thin films.
本発明の方法においては、前記薄膜被形成部材を前述の
ように保持することにより、プラズマかエツジ部に局所
的に集中するのを防止して、膜厚の均一性に優れると共
に剥離の少ないダイヤモンド薄膜および／またはダイヤ
モンド状炭；Ｉ薄膜を製造することかてきる。In the method of the present invention, by holding the member on which the thin film is formed as described above, it is possible to prevent the plasma from locally concentrating on the edge portion, and to achieve excellent film thickness uniformity and less peeling of the diamond. It is possible to produce thin films and/or diamond-like charcoal; I thin films.
前記原料ガスを励起する手段には、気相法によりダイヤ
モンド薄膜および／またはダイヤモンド状炭素薄膜を形
成することのできる方法てあれば特に制限はなく、たと
えば直流または交流アーク放電によりプラズマ分解する
方法、高周波誘導放電によりプラズマ分解する方法、マ
イクロ波放電によりプラズマ分解する方法（ＥＣＲ−Ｃ
ＶＤ法を含む、）あるいはプラズマ分解をイオン室また
はイオン銃で行なわせ、電界によりイオンを引き出すイ
オンビーム法、熱フィラメントによる加熱により熱分解
する熱分解法（Ｅ Ａ ＣＶ Ｄ法を含む。）などのい
ずれをも採用することかできる。The means for exciting the raw material gas is not particularly limited as long as it can form a diamond thin film and/or a diamond-like carbon thin film by a vapor phase method, such as a method of plasma decomposition by direct current or alternating current arc discharge, Plasma decomposition method using high-frequency induced discharge, plasma decomposition method using microwave discharge (ECR-C
(including the VD method), an ion beam method in which plasma decomposition is performed in an ion chamber or an ion gun, and ions are extracted by an electric field, a thermal decomposition method in which thermal decomposition is performed by heating with a hot filament (including the E A CV D method), etc. Either of these can be adopted.
これら各種の励起手段の中でも、特にマイクロ波プラズ
マＣＶＤ法、高周波プラズマＣＶＤ法を採用すると、特
に効果的である。Among these various excitation means, microwave plasma CVD and high frequency plasma CVD are particularly effective.
本発明の方法においては、以下の条件下に反応か進行し
て、プラズマが局所的に集中するのを防止しつつ前記Ｆ
ＩＦＡ被形成部材の前記薄膜被形成面上に、膜厚の均一
性に優れると共に剥離の生じにくいダイヤモンド類薄膜
が析出する。In the method of the present invention, the reaction proceeds under the following conditions, and the F
A diamond-like thin film is deposited on the thin film forming surface of the IFA forming member, which has excellent film thickness uniformity and is difficult to peel off.
すなわち、本発明の方法においては、前記保持部材によ
り保持された前記薄膜被形成部材の温度を、通常、３０
０〜１．３００℃、好ましくは５００〜１．１００℃に
設定する。That is, in the method of the present invention, the temperature of the thin film forming member held by the holding member is usually set at 30°C.
The temperature is set at 0 to 1.300°C, preferably 500 to 1.100°C.
この温度が３００℃より低いと、ダイヤモンド類薄膜の
析出速度が遅くなったり、非硬質炭素を多量に含んだ膜
が形成されることがある。一方。If this temperature is lower than 300° C., the precipitation rate of the diamond-like thin film may be slowed down, or a film containing a large amount of non-hard carbon may be formed. on the other hand.
１．１００℃より高くしても、それに見合った効果は奏
されず、エネルギー効率の点で不利となる。1. Even if the temperature is higher than 100°C, no commensurate effect will be achieved and this will be disadvantageous in terms of energy efficiency.
本発明の方法においては、成膜段階において前記薄膜被
形成部材の温度を前記の範囲で変更してもよいが１通常
は一定に保つことが好ましい。特に前記薄膜被形成部材
の温度分布を前記の範囲で一定に保つと、膜厚の均一性
がさらに優れたダイヤモンド類薄膜を得ることができる
。In the method of the present invention, the temperature of the member on which the thin film is to be formed may be changed within the above range in the film forming step, but it is generally preferable to keep it constant. In particular, by keeping the temperature distribution of the member on which the thin film is formed constant within the above range, a diamond-like thin film with even better film thickness can be obtained.
反応圧力は、通常、１０−６〜１０３Ｌｏｒｒ、好まし
くは１０−’ｔｏｒｒ〜７６０ｔ、ｏｒｒである。The reaction pressure is usually 10-6 to 103 Lorr, preferably 10-'torr to 760 t, orr.
たたし１本発明の方法において１反応圧力をｌ Ｌｏｒ
ｒよりも低く設定する場合には１反応室内に磁場を加え
た状態で、前記原料ガスを励起するのが好ましい、した
がって、この場合には、前記原料ガスの励起手段にＥＣ
Ｒ（電子サイクロトロン）−ＣＶＤ法を好適に採用する
ことかできる。In the method of the present invention, the reaction pressure is 1 Lor
When setting the value lower than r, it is preferable to excite the raw material gas while applying a magnetic field within one reaction chamber. Therefore, in this case, the excitation means for the raw material gas is
R (electron cyclotron)-CVD method can be suitably employed.
反応圧力がＩｎ−６ｔｏｒｒよりも低いと、ダイヤモン
ド類ｉ１［Ｉｌ！２の析出速度か遅くなったり、ダイヤ
モンド類１［か析出しなくなったりすることかある。When the reaction pressure is lower than In-6 torr, diamonds i1 [Il! The precipitation rate of diamonds 2 may slow down, or diamonds 1 may no longer precipitate.
一方、 １０’ ｔｏｒｒより高くしてもそれに見合っ
た効果は奏されないことかある。On the other hand, even if the torque is set higher than 10' torr, the corresponding effect may not be achieved.
反応時間は、薄膜被形成部材の温度、反応圧力、必要と
する膜厚などにより相違するので一部に決定することは
てきないか、通常は、５時間以内とすることができる。Since the reaction time varies depending on the temperature of the member on which the thin film is to be formed, the reaction pressure, the required film thickness, etc., it cannot be determined in part, but usually it can be set to within 5 hours.
本発明の方法によると、プラズマの局所的な集中を防止
して、膜厚の均一性に優れて剥離の生じにくい高品質の
ダイヤモンド類薄膜を高速成膜により効率良く製造する
ことができる。According to the method of the present invention, local concentration of plasma can be prevented, and a high-quality diamond-based thin film with excellent film thickness uniformity and less likely to peel off can be efficiently produced by high-speed film formation.
このようにして得られるダイヤモンド類薄膜は、特に切
削工具類に好適に利用可能であるばかりではなく、たと
えば耐摩耗性機械部品等の各種部材のハードコーティン
グ材や電子材料などに好適に利用可ｒ針である。The diamond-like thin film obtained in this way can be used not only particularly suitably for cutting tools, but also for hard coating materials for various parts such as wear-resistant mechanical parts, electronic materials, etc. It's a needle.
そして、前述の製造方法に３いては、請求項２または請
求項３に記載の製造装置を好適に使用することかできる
。In the third manufacturing method described above, the manufacturing apparatus according to claim 2 or 3 can be suitably used.
請求項２に記載の製造装とは、薄膜被形成部材を保持す
る開口部を有すると共に、前記薄膜被形成部材の薄膜被
形成面と同一面を形成する開口部開設面を有する保持部
材と、放電装置とを備えるものである。The manufacturing equipment according to claim 2 includes a holding member having an opening for holding a thin film forming member and having an opening opening surface that forms the same surface as a thin film forming surface of the thin film forming member; A discharge device is provided.
第２図に本発明の製造装置の一例であるマイクロ波プラ
ズマＣＶＤ装置を示す。FIG. 2 shows a microwave plasma CVD apparatus which is an example of the manufacturing apparatus of the present invention.
第２図に示したように、本発明の製造装置は、薄膜被形
成部材ｌを保持する開口部３を有する保持部材２と、マ
イクロ波発振器４とを備える。As shown in FIG. 2, the manufacturing apparatus of the present invention includes a holding member 2 having an opening 3 for holding a thin film forming member l, and a microwave oscillator 4.
そして、保持部材２の開口部開設面５に開設される開口
部３は、ｖｉ膜脱液成部材ｌを収納可能な大きさに形成
してあり、薄膜被形成部材ｌは、この開口部３内で、薄
膜被形成部材１の薄膜被形成面１０と、開口部開設面５
とが同一面を形成するように保持される。The opening 3 opened in the opening opening surface 5 of the holding member 2 is formed in a size that can accommodate the VI membrane deliquid forming member l, and the thin film forming member l is placed in the opening 3. The thin film forming surface 10 of the thin film forming member 1 and the opening opening surface 5
are held so that they form the same plane.
ここで、開口部３は、ｔ５２図に示したように、保持部
材２の一部に一方のみが開口するように形成されたもの
であってもよいし、たとえば第３図に示した請求項３に
記載の製造装置におけるように、貫通孔３５により形成
されたものであってもよい、第３図に示した請求項３に
記載の製造装置においては、開口部３が貫通孔３５であ
るので、保持部材２の両面から薄膜被形成部材ｌを開口
部３内に収納することができるという利点があるととも
に、保持部材２のみを薄膜被形成部材１に合せて容易に
作成することができるという利点がある。Here, the opening 3 may be formed in a part of the holding member 2 so that only one side is open, as shown in FIG. In the manufacturing apparatus according to claim 3 shown in FIG. Therefore, there is an advantage that the thin film forming member 1 can be stored in the opening 3 from both sides of the holding member 2, and only the holding member 2 can be easily created to match the thin film forming member 1. There is an advantage.
また、開口部３の形状は、少なくとも薄膜被形成部材ｌ
の穂膜被形成面１０と保持部材２の開口部開設面５とが
同一面を形成することのできる形状であれば特に制限は
なく、たとえば四角形、三角形、および切削ドリルの刃
先の形状等にすることができる。Further, the shape of the opening 3 is such that at least the thin film forming member l
There is no particular restriction on the shape as long as the surface 10 on which the ear membrane is formed and the opening surface 5 of the holding member 2 can form the same surface, such as a square, a triangle, or the shape of the cutting edge of a cutting drill. can do.
前述のような機能を有する前記保持部材の形成材料につ
いても、請求項１に記載の方法における反応温度に耐え
ることのできるものであれば特に制限はないが、たとえ
ば前記薄膜被形成部材がＷＣ−Ｃｏ系、宥Ｃ−ＴｉＣ−
Ｃｏ系、ＶｉＣ−ＴｉＣ−ＴａＣ−Ｃｏ系などの超硬合
金からなる場合には、これらの超硬合金を用いるという
ように、前記薄膜被形成部材の形成材料と同一もしくは
類似の物性、特に熱的、電気的物性を有する材料である
ことか好ましい、このような材料であると、保持部材と
薄膜被形成部材との温度、特に温度分布を均一化するこ
とができるからである。したかつて、マイクロ波や高周
波を用いる場合には、誘電率の近似した材料の組合わせ
を選定することが好ましい。いずれにせよ、前記保持部
材の形成材料か、前記が５脱液形成部材の形成材料と同
一もしくは類似の物性を有する材料であると、本発明の
製造装置においてプラズマの局所的な集中をさらに効果
的に防止することかできる。The material for forming the holding member having the above-described function is not particularly limited as long as it can withstand the reaction temperature in the method according to claim 1, but for example, if the thin film forming member is WC- Co-based, comfortable C-TiC-
When the material is made of a cemented carbide such as Co-based or ViC-TiC-TaC-Co-based, the material has the same or similar physical properties as the material for forming the thin film, especially thermal properties. It is preferable that the material has physical and electrical properties, because the temperature, especially the temperature distribution, between the holding member and the member on which the thin film is to be formed can be made uniform. However, when using microwaves or high frequencies, it is preferable to select a combination of materials with similar dielectric constants. In any case, if the holding member is formed of a material having the same or similar physical properties as the forming material of the deliquification forming member 5, the local concentration of plasma can be further improved in the manufacturing apparatus of the present invention. It can be prevented.
かかる構成により、前記原料ガスをプラズマの局所的な
集中を防止しつつ励起することか可１駐てあり、膜厚の
均一性に優れて」離の生じにくいダイヤモンド類薄膜の
高速成膜を達成することができる。With this configuration, it is possible to excite the raw material gas while preventing local concentration of plasma, and achieve high-speed deposition of a diamond-based thin film with excellent film thickness uniformity and resistant to delamination. can do.
したかって、本発明の製造装置は、請求項１の製造方法
において好適に使用可能であり、本発明の製造装置を使
用して製造されるダイヤモンド類薄膜は、膜厚の均一性
に優れて剥離の生じにくいものである。Therefore, the production apparatus of the present invention can be suitably used in the production method of claim 1, and the diamond thin film produced using the production apparatus of the present invention has excellent film thickness uniformity and is easy to peel. It is difficult for this to occur.
［実施例］
次いで、本発明の実施例および比較例を示し、この発明
についてさらに具体的に説明する。[Example] Next, Examples and Comparative Examples of the present invention will be shown to further specifically explain the present invention.
（実施例１）
第３図に示したような構成からなる請求項３に記載のマ
イクロ波プラズマＣＶＤ製造装置を使用して、ＷＣ−６
％Ｃｏ組成を持つ保持部材の開口部（１３，７ｘ １３
．７Ｘ ：１．１８ｓａｌｌ ）に、ＷＣ−６％Ｃｏ組
成を持つ切削チップ（１２，７ｘ １２．７Ｘ ３．１
１ｖＨ）を薄膜被形成部材として収納した。(Example 1) Using the microwave plasma CVD manufacturing apparatus according to claim 3 having the configuration shown in FIG.
% Co composition opening of the holding member (13,7x 13
．． 7X: 1.18sall), cutting tip with WC-6%Co composition (12,7x 12.7X 3.1
1vH) was housed as a member on which a thin film was formed.
次いて１反応室内に水素ガスを７％、−酸化炭素ガスを
９３％の割合で、かつ水素ガスおよび一酸化炭素ガスの
合計流量１００ｓｅｃ＋ｓで導入し、反応室内の圧力４
０ｔｏｒｒ、薄膜被形成部材の温度９（１０℃の条件下
に、周波数２．４５Ｇｌ！ｚのマイクロ波電源の出力を
４００Ｗに設定した。この条件でマイクロ波放電方式に
よるプラズマ処理を５時間行なって、薄膜付き切削チッ
プを製造した。Next, hydrogen gas was introduced into one reaction chamber at a ratio of 7% and -carbon oxide gas at a ratio of 93%, and the total flow rate of hydrogen gas and carbon monoxide gas was 100 sec + s, and the pressure inside the reaction chamber was 4.
Under the conditions of 0 torr and a temperature of 9 (10°C) on the member to be formed with a thin film, the output of a microwave power source with a frequency of 2.45 Gl!z was set to 400 W. Under these conditions, plasma treatment using a microwave discharge method was performed for 5 hours. , produced a cutting tip with a thin film.
なお、切削チップは洗浄剤［日化精工麹製；［ランゲル
ＥＪ］の１０倍稀釈液（液温５０°Ｃ）および純水を６
０秒間に１回の割合て順次に用いて、各々３回ずつの洗
浄を行なってから使用した。In addition, the cutting tip was prepared using a 10-fold diluted solution (liquid temperature 50°C) of a cleaning agent [manufactured by Nikka Seiko Koji; [Langer EJ] and pure water for 60 minutes.
They were used sequentially at a rate of once every 0 seconds, and each was washed three times before use.
反応終了後、この切削チップの薄膜についてラマン分光
分析を行なったところ、１：ｌ：ｌ：１ｅａ−’の位置
にダイヤモンドに起因するシャープなピークか認められ
た。When the thin film of this cutting tip was subjected to Raman spectroscopic analysis after the reaction was completed, a sharp peak due to diamond was observed at the position of 1:l:l:1ea-'.
また、この薄膜の各部のｗ２Ｎは、５〜５．５ｐｍでり
、均一性に優れるものであった。Moreover, the w2N of each part of this thin film was 5 to 5.5 pm, and had excellent uniformity.
さらに、前記と同様の操作により得られたダイヤモンド
Ｑ膜付き切削チップについて、剥離の生じているサンプ
ルの出現率を求めた。Furthermore, the appearance rate of samples in which peeling occurred was determined for the diamond Q film-coated cutting chips obtained by the same operation as described above.
結果を第１表に示す。The results are shown in Table 1.
（比較例１）
前記実施例１において、保持部材を使用しないで、ＷＩ
Ｇ−６％Ｃｏ組成を持つ切削チウブな窒化ホウ素からな
る平板基板上に載置したほかは、前記実施例１と同様に
して薄膜付き切削チップを製造した。(Comparative Example 1) In Example 1, the WI
A cutting tip with a thin film was produced in the same manner as in Example 1, except that it was placed on a flat substrate made of boron nitride, which is suitable for cutting and has a composition of G-6% Co.
反応終了後、この切削チップの薄膜についてラマン分光
分析を行なったところ、１］：１３ｃ■−１の位置にダ
イヤモンドに起因するシャープなピークが認められた。After the reaction was completed, the thin film of the cutting tip was subjected to Raman spectroscopy, and a sharp peak due to diamond was observed at the position 1]:13c-1.
また、この薄膜の各部の膜厚は、４ＩＬｍ（中央部）〜
ｌ：ｌｐｍ（エツジ部）であり、前記実施例１て得られ
たダイヤモンド＠膜付き切削チップに比較して、ダイヤ
モンド薄膜の膜厚の均一性に劣るものであった。In addition, the film thickness of each part of this thin film is 4ILm (center part) ~
1: lpm (edge portion), and the uniformity of the thickness of the diamond thin film was inferior to that of the cutting tip with the diamond film obtained in Example 1.
さらに、前記と同様の操作により得られたダイヤモンド
薄膜Ｊ膜付き切削チップについて、剥離の生じているサ
ンプルの出現率を求めた。Furthermore, the appearance rate of samples in which peeling occurred was determined for the cutting chips with the diamond thin J film obtained by the same operation as above.
結果を第１表に示す。The results are shown in Table 1.
（木頁、以下余白）
第
表
（評価）
実施例１と比較例１との結果から１本発明の製造装置を
使用した本発明の方法によると、プラズマの局所的な集
中がないことを確認した。(Wood page, blank space below) Table (Evaluation) From the results of Example 1 and Comparative Example 1, it was confirmed that there was no local concentration of plasma according to the method of the present invention using the manufacturing apparatus of the present invention. did.
そして、本発明の製造装置を使用した本発明の方法によ
ると、膜厚の均一性に優れ、しかも第１表から明らかな
ように、剥離の生じにくいダイヤモンド類薄膜を得るこ
とができる。According to the method of the present invention using the manufacturing apparatus of the present invention, it is possible to obtain a diamond-like thin film that has excellent film thickness uniformity and is less likely to peel off, as is clear from Table 1.
［発Ｉｊｊの効果］
請求項１に記載の方法によると、
（１） 薄膜被形成部材の薄膜被形成面と保持部材の
表面とか同一面を形成するように保持部材に保持された
６１Ｗ２被形成部材の前記薄膜被形成面に、炭素源ガス
を含有するｊ７料ガスを励起して得られるガスを接触さ
せるので、原料ガスを励起して生しるプラズマか局所的
に集中するのを有効に防止することができて、
（２） プラズマの局所的な集中に起因する膜厚の不
均一化を招くことかないので、熱応力や内部応力が急激
に変化することがなくて、膜厚の均一性に優れ、剥離か
生じにくく、たとえば耐久性に優れた高性能のダイヤモ
ンド類ｆｆＪ膜付き切削工具に好適に利用可能な高品質
のダイヤモンドＱ膜および／またはダイヤモンド状炭素
薄膜を容易に効率良く得ることができる、
という利点を有する工業的に有用なダイヤモンド類薄膜
の製造方法を提供することができる。[Effects of Ijj] According to the method according to claim 1, (1) 61W2 is held by the holding member so that the thin film forming surface of the thin film forming member and the surface of the holding member are the same surface. Since the surface of the member on which the thin film is to be formed is brought into contact with the gas obtained by exciting the raw material gas containing the carbon source gas, it is possible to effectively locally concentrate the plasma generated by exciting the raw material gas. (2) Since there is no possibility of non-uniform film thickness due to local concentration of plasma, there is no sudden change in thermal stress or internal stress, and the film thickness is uniform. To easily and efficiently obtain a high-quality diamond Q film and/or a diamond-like carbon thin film that has excellent properties, is difficult to peel off, and can be suitably used, for example, in a cutting tool with a high-performance diamond-like FFJ film that has excellent durability. It is possible to provide an industrially useful method for manufacturing a diamond thin film having the following advantages.
そして、請求項２または請求項３の発明にょると。According to the invention of claim 2 or claim 3.
（：ｌ） ｆ’ｌ膜被膜成形成部材出することのない
開口部開設面を有する特定の保持部材を備えるので。(:l) Since it is equipped with a specific holding member having an opening surface that does not allow the f'l film forming member to come out.
前述のような利点を有する請求項１に記載の方法におい
て好適に使用可俺である、
という利点を有するダイヤモンド類薄膜の製造袋こを提
供することができる。It is possible to provide a bag for producing diamond-like thin films, which has the advantage of being suitable for use in the method according to claim 1, which has the advantages described above.
第１図は請求項１に記載のダイヤモンド類薄膜の製造方
法における薄膜被形成部材の保持状態の一例を示す断面
図、第２図は請求項２に記載のダイヤモンド類＠膜の製
造装置の一例を示す説明図、：５３図は請求項３に記載
のダイヤモンド類薄膜の製造装置の一例を示す説明図で
ある。
ｌ・・・薄膜被形成部材、２・・・保持部材。
３・・・開口部、４・・・プラズマ発振器。
５・・・開口部開設面、 １０・・・ＩＪ膜膜形形成面
２０・・・ （保持部材の）表面
第１
図
第３図
第２図
手
続
ＷＤ
正
書FIG. 1 is a sectional view showing an example of a holding state of a member on which a thin film is formed in the method for producing a diamond-like thin film according to claim 1, and FIG. 2 is an example of the apparatus for producing a diamond-like film according to claim 2. FIG. 53 is an explanatory diagram showing an example of the apparatus for manufacturing a diamond thin film according to claim 3. 1... Thin film formed member, 2... Holding member. 3...Aperture, 4...Plasma oscillator. 5... Opening opening surface, 10... IJ membrane film forming surface 20... (holding member) surface 1 Figure 3 Figure 2 Procedure WD Ordinary text
Claims (3)
るガスを、薄膜被形成部材の薄膜被形成面と保持部材の
表面とが同一面を形成するべく前記保持部材に保持され
た前記薄膜被形成部材の前記薄膜被形成面に接触させて
、前記薄膜被形成面上にダイヤモンド膜および／または
ダイヤモンド状炭素膜を形成することを特徴とするダイ
ヤモンド類薄膜の製造方法。(1) A gas obtained by exciting a raw material gas containing a carbon source gas is applied to the thin film formed surface of the thin film formed member and the surface of the holding member held by the holding member so that the thin film forming surface of the thin film forming member and the surface of the holding member form the same surface. A method for producing a diamond-like thin film, comprising forming a diamond film and/or a diamond-like carbon film on the thin film forming surface by contacting the thin film forming surface of a thin film forming member.
、前記薄膜被形成部材の薄膜被形成面と同一面を形成す
る開口部開設面を有する保持部材と、放電装置とを備え
ることを特徴とするダイヤモンド類薄膜の製造装置。(2) A holding member having an opening for holding the thin film forming member and having an opening opening face that forms the same surface as the thin film forming surface of the thin film forming member, and a discharge device. A device for producing diamond thin films.
ヤモンド類薄膜の製造装置。(3) The apparatus for manufacturing a diamond thin film according to claim 2, wherein the opening is a through hole.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006292A JPH02188494A (en) | 1989-01-13 | 1989-01-13 | Production of thin film of diamond or the like and device therefor |
| EP90100625A EP0378230A1 (en) | 1989-01-13 | 1990-01-12 | Method of and apparatus for producing diamond thin films |
| KR1019900000370A KR940003099B1 (en) | 1989-01-13 | 1990-01-13 | Method of and apparatus for producing diamond thin films |
| CA002007780A CA2007780A1 (en) | 1989-01-13 | 1990-01-15 | Method of and apparatus for producing diamond thin films |
| US07/813,041 US5258206A (en) | 1989-01-13 | 1991-12-23 | Method and apparatus for producing diamond thin films |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006292A JPH02188494A (en) | 1989-01-13 | 1989-01-13 | Production of thin film of diamond or the like and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02188494A true JPH02188494A (en) | 1990-07-24 |
Family
ID=11634308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1006292A Pending JPH02188494A (en) | 1989-01-13 | 1989-01-13 | Production of thin film of diamond or the like and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02188494A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304249A (en) * | 1990-05-25 | 1994-04-19 | Idemitsu Petrochemical Company Limited | Suscepter device for the preparation of a diamond film-coated body |
| JP2003257648A (en) * | 2002-03-05 | 2003-09-12 | Seiko Epson Corp | Surface treating device, organic el device manufacturing apparatus, organic el device, and electronic apparatus |
| JP2007331955A (en) * | 2006-06-12 | 2007-12-27 | National Institute Of Advanced Industrial & Technology | Method for producing diamond |
| JP2008255437A (en) * | 2007-04-06 | 2008-10-23 | Kobe Steel Ltd | Conductive diamond coated net-like electrode, method of manufacturing the same and ozone water generator provided with the same |
| JP2014237890A (en) * | 2013-05-10 | 2014-12-18 | 国立大学法人電気通信大学 | Film deposition apparatus of diamond-like carbon film and formation method |
-
1989
- 1989-01-13 JP JP1006292A patent/JPH02188494A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304249A (en) * | 1990-05-25 | 1994-04-19 | Idemitsu Petrochemical Company Limited | Suscepter device for the preparation of a diamond film-coated body |
| JP2003257648A (en) * | 2002-03-05 | 2003-09-12 | Seiko Epson Corp | Surface treating device, organic el device manufacturing apparatus, organic el device, and electronic apparatus |
| JP2007331955A (en) * | 2006-06-12 | 2007-12-27 | National Institute Of Advanced Industrial & Technology | Method for producing diamond |
| JP2008255437A (en) * | 2007-04-06 | 2008-10-23 | Kobe Steel Ltd | Conductive diamond coated net-like electrode, method of manufacturing the same and ozone water generator provided with the same |
| JP2014237890A (en) * | 2013-05-10 | 2014-12-18 | 国立大学法人電気通信大学 | Film deposition apparatus of diamond-like carbon film and formation method |
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